JP4572098B2 - Planographic printing plate precursor - Google Patents

Description

  The present invention is a polymerizable photosensitive composition that can be used for image forming materials such as three-dimensional stereolithography, holography, lithographic printing plate materials, color proofs, photoresists and color filters, and photocurable resin materials such as inks, paints, and adhesives. And a lithographic printing plate precursor having a photosensitive layer comprising the photosensitive composition.

Solid-state lasers, semiconductor lasers, and gas lasers that emit ultraviolet light, visible light, and infrared light having a wavelength of 300 nm to 1200 nm are easily available as high-power and small-sized lasers. It is very useful as a recording light source when making a plate directly from data.
Various studies have been made on recording materials sensitive to these various laser beams. As a typical example, a positive recording material described in US Pat. No. 4,708,925 can be used as a material that can be recorded with an infrared laser having a photosensitive wavelength of 760 nm or more. In addition, there are acid-catalyst-crosslinked negative recording materials described in JP-A-8-276558, and US-A-2850445 as a recording material for 300 nm to 700 nm ultraviolet light or visible light laser. And a radical polymerization type negative recording material described in Japanese Patent Publication No. 44-20189.

  On the other hand, short wavelength light of 300 nm or less and an electron beam are particularly important as a photoresist material. In recent years, integrated circuits have become more and more integrated, and in the manufacture of semiconductor substrates such as VLSI, processing of ultra-fine patterns with a line width of less than half a micron is required, and photolithography is used to meet that need. The wavelength used for the exposure apparatus used in the field is increasingly shortened, far ultraviolet light and excimer laser light (XeCl, KrF, ArF, etc.) have been studied, and the formation of ultrafine patterns by electron beams has been studied. In particular, the electron beam is regarded as a promising light source for the next generation pattern forming technology.

A problem common to all of these image forming materials is how to enlarge the ON / OFF of the image in the above-described various energy irradiation portions and non-irradiation portions. That is, it is compatible with high sensitivity and storage stability of the image forming material.
In order to achieve the above-mentioned problems, there are many examples using a highly sensitive photo radical polymerizable composition, and radical polymerizable cross-linking agents and polymer binders are used as the main components of the photo radical polymerizable composition. . In addition, as a radically polymerizable crosslinking agent, a polyfunctional crosslinking agent having two or more polymerizable groups in the molecule is usually used in order to increase the crosslinking efficiency. For example, many are described in Non-Patent Document 1. .
Various compounds containing a photopolymerizable unsaturated group are known and are used in the production of photosensitive recording materials such as printing plates and photoresists. For example, Patent Document 1 discloses a urethane compound which is a reaction product of alkyl diisocyanate, dihydric alcohol and mono (meth) acrylate of dihydric alcohol, and Patent Document 2 discloses a reaction product of glycerol di (meth) acrylate and diisocyanate. Each urethane compound is described. However, the photosensitive recording materials produced using these known polymerizable urethane compounds have certain disadvantages, and all performances of sensitivity, printing durability due to adhesion to the support, and storage stability are provided. A good composition is desired.

On the other hand, recording materials such as lithographic printing plate precursors having a constitution in which a resin layer that is polymerized and cured by light or heat is widely known as an application example of the photoradical polymerizable composition.
In recent years, digitization techniques that electronically process, store, and output image information using a computer have become widespread. Various new image output methods corresponding to such digitization techniques have been put into practical use. Therefore, computer-to-plate (CTP) technology that scans highly directional light such as laser light according to digitized image information and directly manufactures a printing plate without using a lith film is desired. Therefore, obtaining an image recording material adapted to this has become an important technical issue.

As such a scanning exposure-possible recording material, an oleophilic photosensitive resin layer (hereinafter referred to as “photosensitive layer”) containing a photosensitive compound capable of generating active species such as radicals and bronzed acids by laser exposure on a hydrophilic support. A structure provided with a layer is also proposed, and is already on the market as a lithographic printing plate precursor. This lithographic printing plate precursor is laser-scanned based on digital information to generate active species, which causes physical or chemical changes in the photosensitive layer to insolubilize, followed by development processing, so that negative lithographic printing You can get a version.
In particular, a photopolymerization type photosensitive layer (recording layer) containing a photopolymerization initiator excellent in photosensitive speed, an addition-polymerizable ethylenically unsaturated compound, and a binder polymer soluble in an alkali developer on a hydrophilic support. ), And the lithographic printing plate precursor provided with an oxygen-blocking protective layer as necessary is excellent in productivity, is easy to develop, and has desirable printing performance from the advantages of good resolution and inking. It can be a printing plate. When applying the photo-radical polymerizable composition to such a printing plate, it is necessary that the polymerized and cured product after exposure has high strength (high printing durability), and a urethane resin has been conventionally used for the purpose of increasing the strength. Hydrogen bonding interactions such as have been used. However, the use of such hydrogen bond interaction has been problematic in that the film flexibility is lowered and the sensitivity is lowered in order to inhibit radical transfer during polymerization.
"Hardening failure / inhibition factors in UV curing and countermeasures" Technical Information Association JP 63-202740 A Japanese Patent Publication No.2-32293

  Accordingly, it is an object of the present invention to provide a photo-radical polymerization composition that is most promising and promising among image forming techniques, and a polymerizable compound used therefor, with high sensitivity, excellent stability over time, and high printing durability. Is provided, and a lithographic printing plate precursor using the same is provided. In particular, a photosensitive composition suitable as a plate material for lithographic printing capable of direct plate-making from digital data such as a computer by recording using solid-state laser and semiconductor laser light emitting ultraviolet light, visible light and infrared light is provided. There is to do.

As a result of intensive studies to achieve the above object, the present inventor has obtained a photosensitive composition containing a compound having a specific structure (crosslinking agent) in combination with a binder polymer having an amide bond or a urethane bond. The inventors have found that all of high sensitivity, stability over time, and high printing durability can be satisfied, and the present invention has been completed.
That is, the present invention is as follows.

1. (A) a compound represented by the following general formula (I),
(B) a polyurethane containing 10 wt% or more of aromatic groups,
A lithographic printing plate precursor having a photosensitive layer containing a polymerization initiator represented by the following formula I2 and a photosensitive composition containing a thiol or sulfide as a co-sensitizer.

(In the formula, m represents an integer of 2 to 6, l represents an integer of 0 to 6, X represents each independently a divalent linking group, and n represents each independently an integer of 0 or more. Each independently represents a hydrogen atom or a methyl group, and each Z independently represents a monovalent substituent, and when m or l is an integer of 2 or more, X, n, R, Z May be the same or different.)

２．前記感光層上に保護層を有する前記１に記載の平版印刷版原版。
３．前記共増感剤が、２−メルカプトベンゾチアゾール、２−メルカプトベンゾオキサゾール、２−メルカプトベンゾイミダゾール、２−メルカプト−４（３Ｈ）−キナゾリンまたはβ−メルカプトナフタレンである前記１又は２に記載の平版印刷版原版。
４．前記共増感剤が、下記式Ｈ４で表される化合物である前記３に記載の平版印刷版原版。

本発明は、前記１〜４に係る発明であるが、以下、それ以外の事項も含めて記載している。

2. 2. The lithographic printing plate precursor as described in 1 above, which has a protective layer on the photosensitive layer.
3. The lithographic plate according to 1 or 2 , wherein the co-sensitizer is 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, or β-mercaptonaphthalene. A printing plate master.
4). The lithographic printing plate precursor as described in 3 above, wherein the co-sensitizer is a compound represented by the following formula H4.

Although this invention is invention which concerns on said 1-4 , below, other matters are also described.

  The mechanism by which the photosensitive composition containing the compound represented by the above general formula (I) of the present invention as a crosslinking agent can satisfy all of high sensitivity, excellent temporal stability and high printing durability is not clear. However, the specific structure of the crosslinking agent molecule, the high compatibility with the binder polymer having an amide bond or urethane bond used in combination with the crosslinking agent, and the self-aggregation property of the crosslinking agent itself are acting. Conceivable. That is, because of high compatibility with the binder polymer and high self-aggregation property, it is estimated that the crosslinking agent forms ultrafine domains by the crosslinking agent in the binder polymer, and the ultrafine domains are compatible with the binder polymer. The As a result, storage stability is improved, and the disadvantage of radical transfer due to hydrogen bond interaction with the binder polymer is made advantageous by reducing the spatial distance of the polymerizable group, and the tradeoff between high sensitivity and high printing durability is achieved. It is estimated that it has been eliminated.

In addition, the composition of the present invention has not only exposure sensitivity for high sensitivity, but also the temperature dependency usually observed in the polymerization reaction (the polymerization reaction progresses and the curing degree increases by increasing the temperature), and the post-exposure heating The fact that the degree of curing is extremely high without performing operations such as is also a major feature not found in the past.
In particular, a polymerizable composition suitable as a plate material for lithographic printing which can be directly made from digital data such as a computer by recording using solid-state laser and semiconductor laser light emitting ultraviolet light, visible light and infrared light is provided. can do.

  According to the present invention, a combination of a cross-linking agent having a specific structure and a binder polymer having an amide bond or a urethane bond is used so that it has high sensitivity and low temperature dependence, and has excellent storage stability and printing durability. It is possible to satisfy. In particular, a polymerizable composition suitable as a plate material for lithographic printing that can be directly made from digital data such as a computer by recording using a solid-state laser and semiconductor laser light emitting ultraviolet light, visible light and infrared light. Can be provided.

Below, the structural component of the polymerizable photosensitive composition of this invention is demonstrated in detail.
<Crosslinking agent represented by general formula (I) in the present invention>
The photosensitive composition of the present invention contains a compound represented by the following general formula (I), that is, a polyfunctional crosslinking agent having a cyclohexyl group and a plurality of ethylenic polymerizable groups in one molecule.

(In the formula, m represents an integer of 2 to 6, l represents an integer of 0 to 6, X represents each independently a divalent linking group, and n represents each independently an integer of 0 or more. Each independently represents a hydrogen atom or a methyl group, and each Z independently represents a monovalent substituent, and when m or l is an integer of 2 or more, X, n, R, Z May be the same or different.)

Specific examples of X in formula (I) are obtained by removing one hydrogen from an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aryl group, and a substituted aryl group. Divalent linking group, —O—, —S—, —NH—, —NR 1 — (R 1: a monovalent substituent), —CO—, —SO ₂ —, —SO—, or these linking groups And a combination of two or more.

Specific examples of the alkyl group and substituted alkyl group, alkenyl group, substituted alkenyl group, alkynyl group, substituted alkynyl group, aryl group and substituted aryl group include the following.
Examples of the alkyl group include linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, An isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, 2-norbornyl group and the like can be mentioned. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

The substituted alkyl group is composed of a bond between a substituent and an alkylene group, and as the substituent, a monovalent nonmetallic atomic group excluding hydrogen is used. Preferred examples include halogen atoms (—F, —Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkyl Carbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-ary Carbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N'-alkylureido group, N ', N'- Dialkylureido group, N'-arylureido group, N ', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl- N-alkylureido group, N'-alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-
Arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido group, N', N'-diaryl-N- Arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl -N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl Group and its conjugate base group (hereinafter referred to as carboxylate), alkoxy group Bonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkyl Sulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N -Alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-Alky Sulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N-acylsulfamoyl group And its conjugate base group, N-alkylsulfonylsulfamoyl group (—SO ₂ NHSO ₂ (alkyl)) and its conjugate base group, N-arylsulfonylsulfamoyl group (—SO ₂ NHSO ₂ (allyl)) and Conjugated base group, N-alkylsulfonylcarbamoyl group (—CONHSO ₂ (alkyl)) and its conjugate base group, N-arylsulfonylcarbamoyl group (—CONHSO ₂ (allyl)) and its conjugate base group, alkoxysilyl group (—Si (Oalkyl) ₃ ), aryloxysilyl group (—Si (Oallyl) ₃ ), hydroxysilyl group (—Si (O H) ₃ ) and its conjugate base group, phosphono group (—PO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonato group), dialkylphosphono group (—PO ₃ (alkyl) ₂ ), diarylphosphono A group (—PO ₃ (aryl) ₂ ), an alkylarylphosphono group (—PO ₃ (alkyl) (aryl)), a monoalkylphosphono group (—PO ₃ H (alkyl)) and a conjugated base group thereof (hereinafter, Alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugated base group (hereinafter referred to as arylphosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonatooxy group), dialkylphosphono group (-OPO ₃ (alkyl) _2), diaryl phosphono group (-OPO ₃ (aryl) _2), alkylaryl phosphono group (- PO ₃ (alkyl) (aryl)), monoalkyl phosphono group (-OPO ₃ H (alkyl)) and its conjugated base group (hereinafter referred to as alkylphosphonato group), monoarylphosphono group (- OPO ₃ H (aryl)) and its conjugated base group (hereinafter referred to as aryl phosphite Hona preparative group), a cyano group, a nitro group, a hydroxyl group, an aryl group, an alkenyl group, an alkynyl group.

Specific examples of the alkyl group in these substituents include the above-described alkyl groups, and specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group, and a cumenyl group. , Fluorophenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl Group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, phenoxycarbonylphenyl group, N-phenylcarbamoyl group Group, a phenyl group, nitrophenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group, and the like phosphonium Hona preparative phenyl group. Examples of the alkenyl group include vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group and the like. Examples of alkynyl group include ethynyl group, 1- Examples include propynyl group, 1-butynyl group, trimethylsilylethynyl group, phenylethynyl group and the like.

^'The (CO-, R 4 above acyl group R ^4)' can be exemplified hydrogen atom and the above alkyl group, an aryl group, an alkenyl group, an alkynyl group.

  Specific examples of preferred substituted alkyl groups include chloromethyl, bromomethyl, 2-chloroethyl, trifluoromethyl, methoxymethyl, methoxyethoxyethyl, allyloxymethyl, phenoxymethyl, methylthiomethyl, Ruthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N- Methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, methoxycarbonylmethyl group, methoxycarbonylbutyl group, ethoxycarbonyl Bonylmethyl group, butoxycarbonylmethyl group, allyloxycarbonylmethyl group, benzyloxycarbonylmethyl group, methoxycarbonylphenylmethyl group, trichloromethylcarbonylmethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N- Methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, sulfopropyl group, sulfobutyl group, sulfonatobutyl group, sulfur Famoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphono Nyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl Group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1- Examples thereof include a propenylmethyl group, a 2-butenyl group, a 2-methylallyl group, a 2-methylpropenylmethyl group, a 2-propynyl group, a 2-butynyl group, a 3-butynyl group, and the following groups.

  Examples of the aryl group include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include a phenyl group, naphthyl A group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, a fluorenyl group, and the like. Among these, a phenyl group and a naphthyl group are more preferable.

  The substituted aryl group is a group in which the substituent is bonded to the aryl group, and those having a monovalent non-metallic atomic group excluding hydrogen as a substituent on the ring-forming carbon atom of the aryl group described above are used. Examples of preferred substituents include the alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group.

  Preferred examples of these substituted aryl groups include biphenyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, fluorophenyl, chloromethylphenyl, trifluoromethylphenyl, hydroxy Phenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, phenylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxy Phenyl group, benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoyla Nophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) ) Carbamoylphenyl group, N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfa Moylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenyl Ruphosphonophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallylphenyl group 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group, and the like.

Examples of alkenyl groups include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-1-ethenyl, etc. Examples of alkynyl include ethynyl, 1-propynyl. Group, 1-butynyl group, trimethylsilylethynyl group and the like.
The substituted alkenyl group is a group in which the substituent is replaced and bonded to a hydrogen atom of the alkenyl group, and as the substituent, the substituent in the above-mentioned substituted alkyl group is used, while the alkenyl group uses the above-mentioned alkenyl group. Can do. Examples of preferred substituted alkenyl groups include the groups shown below.

  A substituted alkynyl group is one in which the substituent replaces and bonds to a hydrogen atom of the alkynyl group. As the substituent, the substituent in the above-described substituted alkyl group is used, while the alkynyl group uses the above-described alkynyl group. be able to.

  Examples of the monovalent substituent R1 include the same substituents as those described above for the substituted alkyl group.

  As monovalent substituent Z, the thing similar to the substituent in the above-mentioned substituted alkyl group is mentioned.

The divalent linking group X preferably has at least one amide bond, urethane bond, or urea bond in order to improve the interaction with the binder polymer having an amide bond or a urethane bond.
m is more preferably 2 from the balance between sensitivity and stability.
n is preferably 0 or 1 from the viewpoint of compatibility with the binder.
In addition, when l is 1 or more, it is preferable from a compatible viewpoint with a binder that the substituent-[Z] on a cyclohexyl group and the group shown below are not substituted on the same carbon.

  Specific examples of the compound represented by formula (I) used in the present invention are shown below, but the present invention is not limited thereto.

  The compound represented by formula (I) is more preferably formula (II) from the viewpoint of further improving sensitivity.

  (In the formula, m represents an integer of 2 or more, 6 or less, l represents an integer of 0 or more and 6 or less, X ′ independently represents a divalent linking group, and Y independently represents an oxygen atom or —NH—, each independently represents an integer of 0 or more, R represents each independently a hydrogen atom or a methyl group, and each Z independently represents a monovalent substituent, m or l When X is an integer of 2 or more, X ′, Y, n, R, and Z may be the same or different.)

Specific examples of X ′ in the general formula (II) include the same as the specific examples of X in the general formula (I).
Examples of the monovalent substituent Z include those similar to the examples of the substituent in the substituted alkyl group in the specific examples of X described above.
m is more preferably 2 from the balance between sensitivity and stability.
n is preferably 0 or 1, more preferably 1, from the viewpoint of compatibility with the binder.
In addition, when l is 1 or more, it is preferable from a compatible viewpoint with a binder that the substituent-[Z] on a cyclohexyl group and the group shown below are not substituted on the same carbon.

  Furthermore, in order to improve the interaction with a binder having an amide bond or a urethane bond, it is preferable that the general formula (II) has at least one amide bond, urethane bond or urea bond, and in particular, a urethane bond. It is more preferable to have at least one or more.

  Specific examples of the compound represented by the general formula (II) are shown below, but the present invention is not limited thereto.

  Regarding the usage method of the compound represented by these general formula (I), it can set arbitrarily suitably by the performance design of a photosensitive material. A larger amount of the cyclohexyl group-containing compound is usually advantageous in terms of photosensitivity. For example, when used as a photosensitive layer material of a lithographic printing plate precursor, it is preferably 5 to 100 parts by weight of the photosensitive layer component. It is 80 mass parts, More preferably, it is 10-70 mass parts, Most preferably, it is the range of 15-65 mass parts. Sufficient photosensitivity can be obtained within the above range. Moreover, you may use the compound represented by general formula (I) in combination of 2 or more types.

<Binder polymer having amide bond or urethane bond in the present invention>
The photosensitive composition of the present invention further comprises a binder polymer having an amide bond or a urethane bond in addition to the crosslinking agent represented by the above general formula (I) (hereinafter sometimes referred to as a specific cyclohexyl group-containing compound). Containing. Here, the binder polymer having an amide bond or a urethane bond is preferably a linear organic high molecular polymer having an amide bond or a urethane bond. Any of such “linear organic polymer having amide bond or urethane bond” may be used. A linear organic high molecular polymer having an amide bond or a urethane bond that is soluble or swellable in water or weak alkaline water that enables water development or weak alkaline water development is preferably selected. The linear organic high molecular polymer having an amide bond or a urethane bond is selected and used not only as a film-forming agent for the composition but also according to the use as water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development is possible. As such a linear organic polymer having an amide bond or a urethane bond, for example, a binder having an amide group described in JP-A No. 11-171907 is suitable because it has both excellent developability and film strength.
In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent Laid-Open No. 63-287947, Japanese Patent Laid-Open No. The urethane-based binder polymer containing an acid group described in each publication of Japanese Patent No. 271741 and Japanese Patent Application No. 10-116232 is extremely excellent in strength, in terms of printing durability and suitability for low exposure. It is advantageous.

  Furthermore, the above-mentioned specific cyclohexyl group-containing compound is particularly preferred when used in combination with a urethane binder because it has a large effect of improving printing durability, and it is more preferred to use a polyurethane containing 10 wt% or more of aromatic groups.

  In a preferred embodiment of the present invention, a binder having an amide bond or a urethane bond that is substantially water-free and soluble in alkali is used. By doing so, an organic solvent that is not environmentally preferable is not used as the developer, or the amount can be limited to a very small amount. In such usage, the acid value of the binder polymer (the acid content per gram of the polymer expressed as a chemical equivalent number) and the molecular weight are appropriately selected from the viewpoints of image strength and developability. The preferred acid value of the binder polymer is 0.4 to 3.0 meq / g, the preferred molecular weight is in the range of 3000 to 500,000 in terms of mass average molecular weight, more preferably the acid value is 0.6 to 2.0, The molecular weight is in the range of 10,000 to 300,000.

  In the photosensitive composition of the present invention, a known binder polymer can be used in addition to the specific binder resin having an amide bond or a urethane bond. Examples of such known binders include addition polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54- 25957, JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, ie, methacrylic acid copolymer, acrylic acid copolymer, Examples thereof include an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partially esterified maleic acid copolymer. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group are useful.

In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful. These linear organic high molecular polymers can be mixed in an arbitrary amount in the entire composition. Preferably it is 30-85 mass%. The photopolymerizable compound having an ethylenically unsaturated double bond and the linear organic high molecular weight polymer are preferably in the range of 1/9 to 7/3 by mass ratio. In a preferred embodiment, a binder polymer that does not require water and is soluble in alkali is used. By doing so, an organic solvent that is not environmentally preferable is not used as the developer, or the amount can be limited to a very small amount.

  The specific cyclohexyl group-containing compound is preferably used in combination with the specific dye described in JP-A No. 2001-100412, since the starting efficiency is improved and the sensitizing effect is enhanced. Further, in application number 2003-131847 It is more preferable to use together with the specific dye described.

  In the photosensitive composition of the present invention, the specific cyclohexyl group-containing compound is preferably used in combination with the following co-sensitizer because the generated radical species react efficiently and the sensitization effect is enhanced. Since a synergistic effect is acquired by using the following compound together, it is preferable.

  As content of the binder polymer used for this invention, 5-80 mass% is preferable with respect to the composition whole composition, 10-70 mass% is more preferable, 15-65 mass% is the most preferable.

(Addition polymerizable compound)
The photosensitive composition of the present invention may be further mixed with a conventionally known compound having an ethylenically unsaturated bond capable of addition polymerization. The conventionally known compound having an ethylenically unsaturated bond capable of addition polymerization is selected from, for example, compounds having at least one ethylenically unsaturated bond, preferably two or more. Such compound groups are widely known in the industrial field, and these can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, unsaturated carboxylic acid ester having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, amide and monofunctional or polyfunctional isocyanate, addition reaction product of epoxy, monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, an unsaturated carboxylic acid ester having an electrophilic substituent such as an isocyanato group or an epoxy group, an addition reaction product of an amide with a monofunctional or polyfunctional alcohol, an amine or a thiol, a halogen group Also suitable are substitution reaction products of unsaturated carboxylic acid esters, amides with monofunctional or polyfunctional alcohols, amines, and thiols having a leaving substituent such as a tosyloxy group. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol di Acrylate, Tetraethylene glycol diacrylate, Pentaerythritol diacrylate, Pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, etc. .

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (acryloxyethoxy) phenyl] dimethylmethane. Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate Sorbitol tetritaconate and the like.

Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.
Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, and JP-A-59-5240. Those having an aromatic skeleton described in JP-A-59-5241 and JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are also preferably used.

Furthermore, the mixture of the above-mentioned ester monomer can also be mentioned.
Specific examples of an amide monomer of an aliphatic polyvalent amine compound and an unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexa. Examples include methylene bis-methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.

  Other examples include vinyls containing a hydroxyl group represented by the following general formula (C) in a polyisocyanate compound having two or more isocyanate groups per molecule described in JP-B-48-41708. Examples thereof include a vinylurethane compound containing two or more polymerizable vinyl groups in one molecule to which a monomer is added.

^{_{CH 2 = C (R 1)}} COOCH 2 CH (R 2) OH (C)
(However, R ¹ and R ² each independently represent H or CH _3. )

  Also, urethane acrylates as described in JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid can be used. Furthermore, Journal of Japan Adhesion Association vol.20, No. 7, pages 300 to 308 (1984) as photocurable monomers and oligomers can also be used. In the present invention, these monomers can be used in a chemical form such as a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof.

  For these addition-polymerizable compounds, details of how to use, such as what type of structure to use, whether to use alone or in combination, how much is added, etc., according to the performance design of the final photosensitive material, Can be set arbitrarily. For example, it is selected from the following viewpoints. From the viewpoint of photosensitive speed, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the image portion, that is, the cured film, those having three or more functionalities are preferable, and furthermore, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrenic compound, vinyl ether type). A method of adjusting both photosensitivity and strength by using the compound) together is also effective. A compound having a large molecular weight or a compound having a high hydrophobicity is not preferable in terms of development speed and precipitation in a developing solution, although it is excellent in photosensitive speed and film strength. In addition, the selection and use method of the addition polymerization compound is also an important factor for the compatibility and dispersibility with other components in the photosensitive layer (for example, binder polymer, initiator, colorant, etc.). The compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected for the purpose of improving the adhesion of the support, overcoat layer and the like. Regarding the compounding ratio of the addition polymerizable compound in the photosensitive layer, a larger amount is more advantageous in terms of sensitivity, but if it is too much, an undesirable phase separation occurs or a problem in the production process due to the adhesiveness of the photosensitive layer. For example, problems such as transfer of photosensitive material components and manufacturing defects due to adhesion, and precipitation from a developer may occur. From these viewpoints, the preferable blending ratio is often 5 to 80% by mass, preferably 25 to 75% by mass with respect to the total components of the composition. These may be used alone or in combination of two or more. In addition, the use method of the addition polymerizable compound can be arbitrarily selected from the viewpoint of polymerization inhibition with respect to oxygen, resolution, fogging, refractive index change, surface adhesiveness, etc. Depending on the case, a layer configuration and coating method such as undercoating and overcoating can be performed.

(Polymerization initiator)
Moreover, it is preferable to use a polymerization initiator for the polymerizable photosensitive composition of the present invention.
Preferred polymerization initiators include (a) aromatic ketones, (b) aromatic onium salt compounds, (c) organic peroxides, (d) thio compounds, (e) hexaarylbiimidazole compounds, (f) keto Examples include oxime ester compounds, (g) borate compounds, (h) azinium compounds, (i) metallocene compounds, (j) active ester compounds, and (k) compounds having a carbon halogen bond.

(A) Preferable examples of aromatic ketones include compounds having a benzophenone skeleton or a thioxanthone skeleton described in “RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY” J.P.FOUASSIER J.F.RABEK (1993), p77-117, for example,

Etc. More preferable examples of (a) aromatic ketones include α-thiobenzophenone compounds described in JP-B-47-6416, benzoin ether compounds described in JP-B-47-3981, and α-substituted benzoin compounds described in JP-B-47-22326. Benzoin derivatives described in JP-B-47-23664, aroylphosphonic acid esters described in JP-A-57-30704, dialkoxybenzophenones described in JP-B-60-26483, JP-B-60-26403, Benzoin ethers described in JP-A-62-81345, α-aminobenzophenones described in US Pat. No. 4,318,791, European Patent 0284561A1, for example,

P-di (dimethylaminobenzoyl) benzene described in JP-A-2-21152, thio-substituted aromatic ketone described in JP-A-61-194062, acylphosphine sulfide described in JP-B-2-9597, No. 2-9596, for example,

Examples thereof include thioxanthones described in JP-B 63-61950, and coumarins described in JP-B 59-42864.

  Another example of the (b) aromatic onium salt is a group V, VI or VII element of the periodic table, specifically N, P, As, Sb, Bi, O, S, Se. , Te, or I aromatic onium salts. Examples of such aromatic onium salts include compounds disclosed in Japanese Patent Publication No. 52-14277, Japanese Patent Publication No. 52-14278, and Japanese Patent Publication No. 52-14279. In particular,

Can be mentioned.
Furthermore, the following diazonium salts can also be mentioned.

  Another example of the polymerization initiator used in the present invention (c) “organic peroxide” includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule. 3,3′4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3′4,4′-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3′4 , 4'-tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-octylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (kumi Luperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, di-t-butyldiperoxyisophthal Peroxide ester such as chromatography bets are preferable.

  The (d) thio compound as a polymerization initiator used in the present invention is represented by the following general formula [II].

(Wherein R ²⁰ represents an alkyl group, an aryl group or a substituted aryl group, R ²¹ represents a hydrogen atom or an alkyl group, and R ²⁰ and R ²¹ are bonded to each other to form an oxygen, sulfur and nitrogen atom. (A group of nonmetallic atoms necessary to form a 5-membered to 7-membered ring which may contain a selected heteroatom.)
As the alkyl 0 group in the general formula [II], those having 1 to 4 carbon atoms are preferable. As the aryl group, those having 6 to 10 carbon atoms such as phenyl and naphthyl are preferable, and as the substituted aryl group, a halogen atom such as a chlorine atom and an alkyl such as a methyl group as described above. And those substituted with an alkoxy group such as a group, a methoxy group, and an ethoxy group. R ²¹ is preferably an alkyl group having 1 to 4 carbon atoms.

  As other examples of the polymerization initiator used in the present invention, (e) hexaarylbiimidazole includes lophine dimers described in JP-B Nos. 45-37377 and 44-86516, such as 2,2 '-Bis (o-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole Imidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5 5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis ( o- Trophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2 Examples include '-bis (o-trifluorophenyl) -4,4', 5,5'-tetraphenylbiimidazole.

Other examples of the polymerization initiator used in the present invention include (f) ketoxime esters such as 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, and 3-propionyloxyimino. Butan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-p- Toluenesulfonyloxyiminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like can be mentioned.
Examples of the (g) borate salt that is another example of the polymerization initiator in the present invention include compounds represented by the following general formula [III].

(Wherein R ²² , R ²³ , R ²⁴ and R ²⁵ may be the same or different from each other, and each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, A substituted or unsubstituted alkynyl group or a substituted or unsubstituted heterocyclic group, R ²² , R ²³ , R ²⁴ and R ²⁵ may be combined with each other to form a cyclic structure; Provided that at least one of R ²² , R ²³ , R ²⁴ and R ²⁵ is a substituted or unsubstituted alkyl group, and Z ⁺ represents an alkali metal cation or a quaternary ammonium cation). Examples of the alkyl group for R ^{22 to} R ²⁵ include linear, branched, and cyclic groups, and those having 1 to 18 carbon atoms are preferable. Specifically, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, stearyl, cyclobutyl, cyclopentyl, cyclohexyl and the like are included. Examples of the substituted alkyl group include the above alkyl groups, halogen atoms (for example, —Cl, —Br, etc.), cyano groups, nitro groups, aryl groups (preferably phenyl groups), hydroxy groups,

(Wherein R ²⁶ and R ^{27 each} independently represents a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an aryl group), —COOR ²⁸ (where R ²⁸ is a hydrogen atom, having 1 to 14 carbon atoms) An alkyl group or an aryl group), -OCOR ²⁹ or -OR ³⁰ (wherein R ²⁹ and R ³⁰ represent an alkyl group having 1 to 14 carbon atoms or an aryl group) as a substituent. included. The aryl groups of R ^{22 to} R ²⁵ include 1 to 3 ring aryl groups such as a phenyl group and a naphthyl group, and the substituted aryl group is a substitution of the above substituted alkyl group with the above aryl group. Those having a group or an alkyl group having 1 to 14 carbon atoms are included. Examples of the alkenyl group of R ^{22 to} R ²⁵ include linear, branched, and cyclic groups having 2 to 18 carbon atoms, and examples of the substituent of the substituted alkenyl group include the substituents of the substituted alkyl group. Is included. Examples of the alkynyl group of R ^{22 to} R ²⁵ include linear or branched groups having 2 to 28 carbon atoms, and examples of the substituent of the substituted alkynyl group include those listed as the substituents of the substituted alkyl group. included. In addition, examples of the heterocyclic group of R ^{22 to} R ²⁵ include a 5-membered or more, preferably 5 to 7-membered heterocyclic group containing at least one of N, S, and O. May contain a condensed ring. Furthermore, you may have what was mentioned as a substituent of the above-mentioned substituted aryl group as a substituent. Specific examples of the compound represented by the general formula [III] are described in U.S. Pat. Nos. 3,567,453 and 4,343,891 and European Patents 109,772 and 109,773. Examples include compounds and those shown below.

  Examples of the (h) azinium salt compound which is another example of the polymerization initiator of the present invention include JP-A 63-138345, JP-A 63-142345, JP-A 63-142346, JP-A 63-143346. Examples thereof include compounds having an N—O bond described in JP-A 63-143537 and JP-B 46-42363.

  Examples of (i) metallocene compounds which are other examples of polymerization initiators include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, Examples thereof include titanocene compounds described in JP-A-2-4705 and iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109.

  Specific examples of the titanocene compound include di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, and di-cyclopentadienyl-Ti-bis-2,3. 4,5,6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti- Bis-2,4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4 -Difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti- -2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyridin-1-yl) phenyl) titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (methylsulfonamido) phenyl] titanium, bis (cyclopenta And dienyl) bis [2,6-difluoro-3- (N-butylbialoyl-amino) phenyl] titanium.

  Examples of the active ester compound (j) which is another example of the polymerization initiator include imide sulfonate compounds described in JP-B-62-2223, JP-A-63-14340, and JP-A-59-174831. Mention may be made of active sulfonates.

  Preferable examples of the compound (k) having a carbon halogen bond as an example of the polymerization initiator include those represented by the following general formulas [IV] to [X].

(Represented in the formula, X ² is .Y ² represents a halogen atom _{^{-C (X 2) 3, -NH}} 2, -NHR 32, -NR 32, an -OR ^32. Wherein R ³² is an alkyl group, a substituted An alkyl group, an aryl group, or a substituted aryl group, and R ³¹ represents —C (X ² ) ₃ , an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group.

(However, R ³³ is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a halogen atom, an alkoxy group, a substituted alkoxyl group, a nitro group, or a cyano group, and X ³ is a halogen atom. And n is an integer of 1 to 3.)

(However, R ³⁴ is an aryl group or a substituted aryl group, and R ³⁵ is

Or Z ² is —C (═O) —, —C (═S) — or —SO ₂ —, and R ³⁶ and R ³⁷ are alkyl groups, substituted alkyl groups, alkenyl groups, substituted alkenyl groups. , An aryl group or a substituted aryl group, R ³⁸ is the same as R ³² in the general formula [IV], X ³ is a halogen atom, and m is 1 or 2. ) A compound represented by

(Wherein, R ³⁹ is an optionally substituted aryl group or heterocyclic group, R ⁴⁰ is a trihaloalkyl group or trihaloalkenyl group having 1 to 3 carbon atoms, p is 1, 2 or 3.)

Wherein L is a hydrogen atom or a substituent of the formula: CO- (R ⁴¹ ) q (C (X ⁴ ) ₃ ) r, Q is a sulfur, selenium or oxygen atom, a dialkylmethylene group, an alkene-1,2 -Irene group, 1,2-phenylene group or N-R group, M is a substituted or unsubstituted alkylene group or alkenylene group, or 1,2-arylene group, R ⁴² is an alkyl group, An aralkyl group or an alkoxyalkyl group, R ⁴¹ is a carbocyclic or heterocyclic divalent aromatic group, X ⁴ is a chlorine, bromine or iodine atom, and q = 0 and r = 1 Or q = 1 and r = 1 or 2.) A carbonylmethylene heterocyclic compound having a trihalogenomethyl group.

(However, X ⁵ is a halogen atom, t represents an integer of 1 to 3, s is an integer of 1 to 4, R ⁴³ is a hydrogen atom or a CH _3-t X _5t group, R ⁴⁴ is 4-halogeno-5- (halogenomethyl-phenyl) -oxazole derivative represented by s-valent unsaturated organic group which may be substituted.

(However, X ⁶ is a halogen atom, v represents an integer of 1 to 3, u is an integer of 1 to 4, R ⁴⁵ is a hydrogen atom or a CH _3-v X _6v group, R ⁴⁶ is a 2- (halogenomethyl-phenyl) -4-halogeno-oxazole derivative represented by a u-valent unsaturated organic group which may be substituted.

  Specific examples of such a compound having a carbon-halogen bond include, for example, compounds described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), such as 2-phenyl 4,6-bis. (Trichloromethyl) -S-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl)- S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (2 ', 4'-dichlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6-bis (trichloromethyl) -S-triazine, 2-n-nonyl-4,6- Bis (trichloromethyl) -S-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -S-triazine and the like can be mentioned. In addition, compounds described in British Patent 1388492, for example, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4-amino-6-trichloromethyl-S-triazine, etc. And compounds described in JP-A-53-133428, such as 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphtho). -1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-to Chloromethyl-S-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine), 2- (acenaphtho-5-yl) -4,6- Examples thereof include bis-trichloromethyl-S-triazine and the compounds described in German Patent 3333724.

  Further, compounds described in J. Org. Chem. 29, 1527 (1964) by FC Schaefer et al., For example, 2-methyl-4,6-bis (tribromomethyl) -S-triazine, 2,4,6-tris ( Tribromomethyl) -S-triazine, 2,4,6-tris (dibromomethyl) -S-triazine, 2-amino-4-methyl-6-tribromomethyl-S-triazine, 2-methoxy-4-methyl- Examples include 6-trichloromethyl-S-triazine. Further, compounds described in JP-A-62-258241 can be exemplified. Furthermore, compounds described in JP-A-5-281728, for example,

Etc. Alternatively, those skilled in the art can easily synthesize them according to the synthesis method described in MP Hutt, EF Elslager and LM Herbel, “Journal of Heterocyclic chemistry”, Vol. The following compound groups that can

Alternatively, compounds such as those described in German Patent 2,641,100, such as 4- (4-methoxy-styryl) -6- (3,3,3-trichloropropenyl) -2-pyrone and 4- (3 4,5-trimethoxy-styryl) -6-trichloromethyl-2-pyrone, compounds described in German Patent No. 3333450, compounds described in German Patent No. 3021590, or described in German Patent No. 3021599 A compound group, etc. can be mentioned.

More preferable examples of the polymerization initiator in the present invention include the above-mentioned (a) aromatic ketones, (b) aromatic onium salts, (c) organic peroxides, (e) hexaarylbiimidazole, (i) ) Metallocene compounds, (k) compounds having a carbon halogen bond, and most preferred examples include aromatic iodonium salts, aromatic diazonium salts, titanocene compounds, trihalomethyl-- represented by the general formula [IV] Mention may be made of S-triazine compounds.
The polymerization initiator in the present invention is suitably used alone or in combination of two or more.

(Sensitizing dye)
The polymerizable photosensitive composition of the present invention preferably contains a sensitizing dye together with the polymerization initiator.
Examples of the sensitizing dye that can be used in the present invention include a spectral sensitizing dye and a dye or pigment that absorbs light from a light source and interacts with a polymerization initiator.

  Preferred spectral sensitizing dyes or dyes include polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbo). Cyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), phthalocyanines (eg, , Phthalocyanine, metal phthalocyanine), porphyrins (eg, tetraphenylporphyrin, central metal-substituted porphyrin), chlorophylls (eg, chlorophyll, chlorophyllin, central metal) Conversion chlorophyll), metal complexes, for example

Anthraquinones, such as (anthraquinone) squalium, such as (squarium), may be mentioned.

More preferred examples of spectral sensitizing dyes or dyes include styryl dyes described in JP-B-37-13034, cationic dyes described in JP-A-62-143044, and quinoxalinium salts described in JP-B-59-24147. New methylene blue compounds described in JP-A No. 64-33104, anthraquinones described in JP-A No. 64-56767, benzoxanthene dyes described in JP-A No. 2-1714, JP-A No. 2-226148 and Acridines described in JP-A-2-226149, pyrylium salts described in JP-B-40-28499, cyanines described in JP-B-46-42363, benzofuran dyes described in JP-A-2-63053, JP-A-2 JP-A-85858, JP-A-2-216154, conjugated ketone dyes, JP-A-57 A dye described in Japanese Patent Publication No. 10605, an azocinnamilidene derivative described in Japanese Patent Publication No. 2-30301, a cyanine dye described in Japanese Patent Application Laid-Open No. 1-287105, Japanese Patent Application Laid-Open No. 62-31844, and Japanese Patent Application Laid-Open No. 62-62. 31848, xanthene dyes described in JP-A-62-143043, aminostyryl ketones described in JP-B-59-28325, merocyanine dyes described in JP-B-61-9621, JP-A-2-179634 A merocyanine dye represented by the following general formula [1] described in JP-A-2-244050,

(Wherein R ⁵⁴ and R ⁵⁵ each independently represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxycarbonyl group, an aryl group, a substituted aryl group or an aralkyl group. A ² represents an oxygen atom, a sulfur atom or a selenium atom. Represents a tellurium atom, an alkyl or aryl-substituted nitrogen atom, or a dialkyl-substituted carbon atom, X ⁹ represents a group of non-metallic atoms necessary to form a nitrogen-containing hetero five-membered ring, and Y ⁴ represents a substituted Z ³ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, an alkoxy group, a phenyl group, an unsubstituted or substituted polynuclear aromatic ring, or an unsubstituted or substituted heteroaromatic ring. group, an alkylthio group, an arylthio group, a substituted amino group, an acyl group or an alkoxycarbonyl group, together with Y ⁴ It may be bonded to form a ring.)
Preferred examples are

Merocyanine dyes represented by the following general formula [2] described in JP-B-59-28326, for example,

In the above formula, R ⁵⁶ and R ⁵⁷ each represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group or an aralkyl group, which may be the same or different from each other. X ¹⁰ represents a substituent having a Hammett's sigma (σ) value in the range of −0.9 to +0.5. Merocyanine dyes represented by the following general formula [3] described in JP-A-59-89303, for example,

(In the formula, each of R ⁵⁸ and R ⁵⁹ independently represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group or an aralkyl group. X ¹¹ has a Hammett sigma (σ) value of − (Y ⁵ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, an acyl group, or an alkoxycarbonyl group.)
As a preferable specific example,

A merocyanine dye represented by the following general formula [4] described in JP-A-8-129257;

(Wherein R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁸ , R ⁶⁹ , R ⁷⁰ , R ⁷¹ are each independently a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted group) Aryl, hydroxyl, substituted oxy, mercapto, substituted thio, amino, substituted amino, substituted carbonyl, sulfo, sulfonate, substituted sulfinyl, substituted sulfonyl, phosphono, substituted phosphono, phosphonate A group, a substituted phosphonate group, a cyano group, a nitro group, or R ⁶⁰ and R ⁶¹ , R ⁶¹ and R ⁶² , R ⁶² and R ⁶³ , R ⁶⁸ and R ⁶⁹ , R ⁶⁹ and R ⁷⁰ , R ⁷⁰ R ⁷¹ may be bonded to each other to form an aliphatic or aromatic ring, R ⁶⁴ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, and R ⁶⁵ is substituted, or Unsubstituted arche Ruarukiru group, or a substituted or unsubstituted alkynylalkyl group, independently R ^66, R ⁶⁷ are each a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a substituted carbonyl group To express)
Preferred examples are

A benzopyran dye represented by the following general formula [5] described in JP-A-8-334897;

(Wherein R ^{72 to} R ⁷⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxy group or an amino group. R ^{72 to} R ⁷⁵ are carbons to which they can be bonded respectively. A ring composed of a non-metal atom may be formed together with an atom, R ⁷⁶ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaromatic group, a cyano group, an alkoxy group, a carboxy group or an alkenyl group, and R ⁷⁷ represents A group represented by R ⁷⁶ or —Z—R ⁷⁶ , wherein Z represents a carbonyl group, a sulfonyl group, a sulfinyl group or an arylene carbonyl group, and R ⁷⁶ and R ⁷⁷ together form a ring composed of a nonmetallic atom; A represents an O atom, S atom, NH or an N atom having a substituent, B represents an O atom, or a group of = C (G1) (G2), G1 and G2 may be the same or different. May be A hydrogen atom, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an arylcarbonyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, or a fluorosulfonyl group, provided that G1 and G2 are the same. G1 and G2 may form a ring composed of a nonmetallic atom together with a carbon atom, and a short wave type ketone-based and styryl-based dye described in EP1048982A1, for example, the following chemical structure) Can be mentioned.

In addition, the following infrared absorbers (dyes or pigments) are also preferably used as sensitizing dyes.
Preferred examples of the dye include cyanine dyes described in JP-A-58-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, and the like. Examples include cyanine dyes described in Japanese Patent No. 434,875.

  Further, near infrared absorption sensitizers described in US Pat. No. 5,156,938 are also preferably used, and further substituted aryl benzoates described in US Pat. No. 3,881,924 are also used. (Thio) pyrylium salt, trimethine thiapyrylium salt described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A 58-181051, 58-220143, 59 -41363, 59-84248, 59-84249, 59-146063, 59-146061, pyranyl compounds described in JP-A-59-216146, cyanine dyes described in US The pentamethine thiopyrylium salt described in Japanese Patent No. 4,283,475, and the like described in Japanese Patent Publication Nos. 5-13514 and 5-19702 That pyrylium compounds are also preferably used.

  In addition, near infrared absorbing dyes described as formulas (I) and (II) in US Pat. No. 4,756,993 and phthalocyanine dyes described in EP 916513A2 are also preferable dyes. Can do.

  Furthermore, the anionic infrared absorber described in Japanese Patent Application No. 10-79912 can also be suitably used. An anionic infrared absorbing agent refers to an anionic infrared absorbing agent having an anionic structure without a cationic structure in the mother nucleus of a dye that substantially absorbs infrared rays. Examples include (c1) anionic metal complexes, (c2) anionic carbon black, (c3) anionic phthalocyanine, and (c4) a compound represented by the following general formula 6. The counter cation of these anionic infrared absorbers is a monovalent cation containing a proton or a polyvalent cation.

  Here, the (c1) anionic metal complex refers to a substance that becomes an anion in the central metal and the entire ligand of the complex part that substantially absorbs light.

  Examples of (c2) anionic carbon black include carbon black to which anionic groups such as sulfonic acid, carboxylic acid, and phosphonic acid groups are bonded as substituents. In order to introduce these groups into carbon black, as described in Carbon Black Handbook 3rd Edition (Edited by Carbon Black Association, April 5, 1995, published by Carbon Black Association), page 12, What is necessary is just to take means, such as oxidizing carbon black.

  (C3) Anionic phthalocyanine refers to a phthalocyanine skeleton bonded with the anionic group previously mentioned in the description of (c2) as a substituent to form an anion as a whole.

Next, the compound represented by (c4) general formula 6 will be described in detail. In Formula 6, G _a ^- represents an anionic substituent, G _b represents a neutral substituent. X ^{m +} represents a 1 to m-valent cation containing a proton, and m represents an integer of 1 to 6. M represents a conjugated chain, and this conjugated chain M may have a substituent or a ring structure. The conjugated chain M can be represented by the following formula.

In the above formula, R ¹ , R ² and R ³ are each independently a hydrogen atom, halogen atom, cyano group, alkyl group, aryl group, alkenyl group, alkynyl group, carbonyl group, thio group, sulfonyl group, sulfinyl group, It represents an oxy group or an amino group, and these may be linked to each other to form a ring structure. n represents an integer of 1 to 8.

  Of the anionic infrared absorbers represented by the general formula 6, those of the following A-1 to A-5 are preferably used.

  Moreover, the cationic infrared absorber shown below can also be used preferably.

In the structural formula, T ⁻ represents a monovalent counter anion, preferably a halogen anion (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ ), a Lewis acid anion (BF ₄ ⁻ , PF ₆ ⁻ , SbCl _6). ⁻ , ClO ₄ ⁻ ), alkylsulfonate anion, and arylsulfonate anion.

  The alkyl of the alkyl sulfonic acid means a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, a butyl group. , Pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, t- A butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, and 2-norbornyl group can be exemplified. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

  The aryl of the aryl sulfonic acid includes one consisting of one benzene ring, two or three benzene rings forming a condensed ring, and one having a benzene ring and a 5-membered unsaturated ring forming a condensed ring. Specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenabutenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable.

  Moreover, the nonionic infrared absorber shown below can also be used preferably.

  Among the exemplified compounds, A-1 is a particularly preferable anionic infrared absorber, and CA-7, CA-18, CA-22, and CA-23 are nonionic infrared absorbers as a cationic infrared absorber. As NA-2.

As other dyes, commercially available dyes and known dyes described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970) can be used. Specifically, azo dyes,
Examples thereof include metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, diimmonium dyes, aminium dyes, squarylium dyes, and metal thiolate complexes.

  As other sensitizing dyes, commercially available pigments and color index (CI) manuals, “Latest Pigment Handbook” (edited by the Japan Pigment Technology Association, published in 1977), “Latest Pigment Applied Technology” ( CMC Publishing, published in 1986), “Printing Ink Technology”, published by CMC Publishing, published in 1984) can be used. For example, types of pigments include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and other polymer-bonded dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments In addition, quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like can be used. Among these pigments, carbon black is preferable.

These pigments may be used without surface treatment, or may be used after surface treatment.
The surface treatment method includes a method of surface coating with a resin or wax, a method of attaching a surfactant, a method of bonding a reactive substance (eg, silane coupling agent, epoxy compound, polyisocyanate, etc.) to the pigment surface, etc. Can be considered. The surface treatment methods are described in “Characteristics and Applications of Metal Soap” (Sachibo), “Printing Ink Technology” (CMC Publishing, 1984) and “Latest Pigment Application Technology” (CMC Publishing, 1986). Yes.

  The particle diameter of the pigment is preferably 0.01 μm to 10 μm, more preferably 0.05 μm to 1 μm, and particularly preferably 0.1 μm to 1 μm. When the particle size of the pigment is 0.01 μm or more, it is preferable from the viewpoint of stability of the dispersion in the image recording layer coating solution, and when it is 10 μm or less, it is preferable from the viewpoint of uniformity of the image recording layer.

  As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production, or the like can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. Details are described in "Latest Pigment Applied Technology" (CMC Publishing, 1986).

Still more preferred examples of the sensitizing dye in the present invention include the merocyanine dye described in JP-B-61-9621, the merocyanine dye described in JP-A-2-17943, and the merocyanine described in JP-A-2-244050. Dyes, merocyanine dyes described in JP-B-59-28326, merocyanine dyes described in JP-A-59-89303, merocyanine dyes described in JP-A-8-129257, and benzopyrans described in JP-A-8-334897 Examples thereof include dyes and short-wave type ketone and styryl dyes described in EP1048982A1.
Furthermore, the infrared absorber of the above-mentioned Unexamined-Japanese-Patent No. 11-209001 can be mentioned.

  The sensitizing dye in the present invention is suitably used alone or in combination of two or more.

"D. Other ingredients"
To the photosensitive composition of the present invention, other components suitable for its use and production method can be added as appropriate. Hereinafter, preferred additives will be exemplified.

(D1) Co-sensitizer The sensitizing dye in the invention is also preferably used alone or in combination of two or more. Furthermore, the polymerizable composition of the present invention may contain a known compound having a function of further improving sensitivity or suppressing inhibition of polymerization by oxygen as a co-sensitizer.

  Examples of such cosensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

  Other examples of co-sensitizers include thiols and sulfides, for example, thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, and JP-A-56 And the like. Specific examples include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene. Etc.

  Other examples include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in Japanese Patent Publication No. 48-42965 (eg, tributyltin acetate), and hydrogen described in Japanese Patent Publication No. 55-34414. Donors, sulfur compounds described in JP-A-6-308727 (eg, trithiane), phosphorus compounds described in JP-A-6-250387 (diethylphosphite, etc.), Si-- described in Japanese Patent Application No. 6-191605 H, Ge-H compound, etc. are mentioned.

The usage-amount of the photoinitiator in the composition in this invention is 0.01-60 mass% with respect to the mass of all the components of a polymeric composition, More preferably, it is 0.05-30 mass%.
Moreover, when using a sensitizing dye in this invention, the molar ratio of the photoinitiator in a polymeric composition and a sensitizing dye is 100: 0 to 1:99, More preferably, it is 90: 10-10: 90. And most preferably 80:20 to 20:80.
When using the above-mentioned co-sensitizer, it is appropriate to use 0.01 to 50 parts by mass with respect to 1 part by mass of the polymerization initiator.

(D2) Polymerization inhibitor In the present invention, in addition to the above basic components, unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond that can be polymerized during the production or storage of the photosensitive composition is prevented. Therefore, it is desirable to add a small amount of a thermal polymerization inhibitor. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol ), 2,2′-methylenebis (4-methyl-6-tert-butylphenol),
N-nitrosophenylhydroxyamine primary cerium salt and the like. The addition amount of the thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the entire composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and it may be unevenly distributed on the surface of the photosensitive layer in the course of drying after coating. . The amount of the higher fatty acid derivative added is preferably about 0.5% by mass to about 10% by mass of the total composition.

(D3) Colorant, etc. Further, a dye or pigment may be added for the purpose of coloring the photosensitive layer. Thereby, so-called plate inspection properties such as visibility after plate making and suitability for an image density measuring machine as a printing plate can be improved. As the colorant, many dyes cause a decrease in the sensitivity of the photopolymerization type photosensitive layer. Therefore, it is particularly preferable to use a pigment as the colorant. Specific examples include pigments such as phthalocyanine pigments, azo pigments, carbon black and titanium oxide, and dyes such as ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes. The addition amount of the dye and the pigment is preferably about 0.5% by mass to about 5% by mass of the total composition.

(D4) Other Additives In addition, known additives such as inorganic fillers, other plasticizers, and oil sensitizers that can improve ink inking on the surface of the photosensitive layer in order to improve the physical properties of the cured film. May be added.

  Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. 10 mass% or less can be added with respect to the total mass of the compound which has an ionic unsaturated double bond, and a binder.

  Further, for the purpose of improving the film strength (printing durability), which will be described later, a UV initiator, a thermal crosslinking agent, or the like can be added to enhance the effect of heating and exposure after development.

  In addition, it is possible to provide an additive and an intermediate layer for improving the adhesion between the photosensitive layer and the support, and improving the development removability of the unexposed photosensitive layer. For example, by adding or undercoating a compound having a relatively strong interaction with the substrate, such as a compound having a diazonium structure or a phosphone compound, adhesion can be improved and printing durability can be increased. By adding or undercoating a hydrophilic polymer such as acid or polysulfonic acid, the developability of the non-image area is improved, and the stain resistance can be improved.

  When apply | coating the polymeric composition of this invention on a support body, it melt | dissolves in various organic solvents and uses it. Solvents used here include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, lactic acid There are ethyl and the like. These solvents can be used alone or in combination. The solid content in the coating solution is suitably 2 to 50% by mass.

The coating amount of the support for the photosensitive layer mainly affects the sensitivity of the photosensitive layer, the developability, the strength of the exposed film, and the printing durability, and is preferably selected as appropriate according to the application. When the coating amount is too small, the printing durability is not sufficient. On the other hand, if the amount is too large, the sensitivity is lowered, it takes time for exposure, and a longer time is required for development processing, which is not preferable. For the lithographic printing plate for scanning exposure which is the main object of the present invention, the coating amount is suitably in the range of about 0.1 g / m ² to about 10 g / m ² in terms of the mass after drying. More preferably from 0.5 to 5 g / m ^2.

"E. Support"
In order to obtain a lithographic printing plate, which is one of the main objects of the present invention, it is desirable to provide the photosensitive layer on a support having a hydrophilic surface. As the hydrophilic support, a conventionally known hydrophilic support used in a lithographic printing plate can be used without limitation. The support used is preferably a dimensionally stable plate, for example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc). , Copper, etc.), plastic films (for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.) Such as paper or plastic film laminated or vapor-deposited with metal, and known physical and chemical treatments suitable for the purpose of imparting hydrophilicity and improving the strength as necessary. May be applied.

  In particular, preferred supports include paper, polyester film or aluminum plate, among which dimensional stability is good, relatively inexpensive, and a surface with excellent hydrophilicity and strength is provided by surface treatment as needed. An aluminum plate which can be used is particularly preferred. A composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in Japanese Patent Publication No. 48-18327 is also preferable.

  A suitable aluminum plate is a pure aluminum plate or an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements, and may also be a plastic film on which aluminum is laminated or vapor-deposited. Examples of foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. The content of foreign elements in the alloy is at most 10% by mass. Particularly suitable aluminum in the present invention is pure aluminum, but completely pure aluminum is difficult to produce in the refining technique, and may contain slightly different elements. Thus, the composition of the aluminum plate applied to the present invention is not specified, and conventionally known and used aluminum plates can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6 mm, preferably 0.15 mm to 0.4 mm, and particularly preferably 0.2 mm to 0.3 mm.

  In the case of a support having a surface of metal, particularly aluminum, roughening (graining) treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluoride zirconate, phosphate, etc., or anodic oxidation treatment, etc. It is preferable that surface treatment is performed.

  The surface roughening treatment of the aluminum plate is performed by various methods. For example, a method of mechanically roughening, a method of electrochemically dissolving and roughening a surface, and a method of selectively dissolving a surface chemically. This is done by the method of As the mechanical method, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, or a buff polishing method can be used. In addition, as an electrochemical surface roughening method, there is a method of performing alternating current or direct current in an electrolytic solution such as hydrochloric acid or nitric acid. Further, as disclosed in JP-A-54-63902, a method in which both are combined can also be used. Further, prior to roughening the aluminum plate, for example, a degreasing treatment with a surfactant, an organic solvent, an alkaline aqueous solution, or the like is performed in order to remove rolling oil on the surface, if desired.

Furthermore, an aluminum plate that has been roughened and then immersed in an aqueous sodium silicate solution can be preferably used. As described in Japanese Examined Patent Publication No. 47-5125, an aluminum plate which has been anodized and then immersed in an aqueous solution of an alkali metal silicate is preferably used. The anodizing treatment is carried out in an electrolytic solution in which an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or a salt solution thereof, or a combination of two or more thereof, is used. This is carried out by passing an electric current using the aluminum plate as an anode.

  Silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective.

  Furthermore, a support body provided with electrolytic grains as disclosed in JP-B-46-27481, JP-A-52-58602 and JP-A-52-30503, the above-mentioned anodizing treatment and sodium silicate A surface treatment combining treatments is also useful.

  Further, those obtained by sequentially performing mechanical surface roughening, chemical etching, electrolytic graining, anodizing treatment and sodium silicate treatment as disclosed in JP-A-56-28893 are also suitable.

  Furthermore, after performing these treatments, water-soluble resins such as polyvinylphosphonic acid, polymers and copolymers having sulfonic acid groups in the side chain, polyacrylic acid, water-soluble metal salts (for example, zinc borate) or Those having a primer such as a yellow dye or an amine salt are also suitable.

  Further, a sol-gel treated substrate in which a functional group capable of causing an addition reaction by a radical as disclosed in JP-A-7-154983 is covalently used.

  Other preferred examples include those in which a water-resistant hydrophilic layer is provided as a surface layer on an arbitrary support. Examples of such a surface layer include a layer composed of an inorganic pigment and a binder described in US Pat. No. 3,055,295 and JP-A-56-13168, and a hydrophilic swelling described in JP-A-9-80744. Examples thereof include sol-gel films made of titanium oxide, polyvinyl alcohol, and silicic acids described in JP-A-8-507727.

  These hydrophilic treatments are performed to make the surface of the support hydrophilic, in order to prevent harmful reaction of the photopolymerizable composition provided thereon, and to improve the adhesion of the photosensitive layer. It is given for the purpose.

"F. Protective layer"
In the lithographic printing plate for scanning exposure, which is a desirable mode of the present invention, it is usually preferable to provide a protective layer on the layer of the photopolymerizable composition in order to perform exposure in the air. Protective layer prevents exposure to oxygen and low molecular weight compounds such as basic substances in the atmosphere that hinder the image formation reaction caused by exposure in the photosensitive layer, allowing exposure in the atmosphere And Therefore, the properties desired for such a protective layer are low permeability of low-molecular compounds such as oxygen, and further, transmission of light used for exposure is not substantially inhibited and adhesion to the photosensitive layer is excellent. And it is desirable that it can be easily removed in the development process after exposure. Such a device for the protective layer has been conventionally devised, and is described in detail in US Pat. No. 3,458,311 and JP-A-55-49729. As a material that can be used for the protective layer, for example, a water-soluble polymer compound that is relatively excellent in crystallinity is preferably used. Specifically, polyvinyl alcohol, polyvinyl pyrrolidone, acidic celluloses, gelatin, gum arabic, Water-soluble polymers such as acrylic acid are known, but among these, the use of polyvinyl alcohol as a main component gives the best results in terms of basic properties such as oxygen barrier properties and development removability.

  The polyvinyl alcohol used for the protective layer may be partially substituted with an ester, an ether, and an acetal as long as it contains an unsubstituted vinyl alcohol unit for having necessary oxygen barrier properties and water solubility. Similarly, some of them may have other copolymer components. Specific examples of polyvinyl alcohol include those having a hydrolysis rate of 71 to 100 mol% and a molecular weight in the range of 300 to 2400 in terms of mass average molecular weight. Specifically, Kuraray Co., Ltd. PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA-HC, PVA-203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-217E, PVA-220E, PVA-224E, PVA-405, PVA- 420, PVA-613, L-8 and the like.

  Components of the protective layer (selection of PVA, use of additives), coating amount, and the like are selected in consideration of fogging, adhesion, and scratch resistance in addition to oxygen barrier properties and development removability. In general, the higher the hydrolysis rate of the PVA used (the higher the content of the unsubstituted vinyl alcohol unit in the protective layer), the thicker the film thickness, the higher the oxygen barrier property, which is advantageous in terms of sensitivity. However, when the oxygen barrier property is extremely increased, there arises a problem that unnecessary polymerization reaction occurs during production and raw storage, and unnecessary fogging and image line thickening occur during image exposure. In addition, adhesion to the image area and scratch resistance are extremely important in handling the plate. Such a coating method for the protective layer is described in detail, for example, in US Pat. No. 3,458,311 and JP-A-55-49729.

  Furthermore, other functions can be imparted to the protective layer. For example, by adding a colorant (such as a water-soluble dye) that is excellent in the transmission of light from 350 nm to 450 nm and that can absorb light of 500 nm or more, which is used for exposure, it is safe light without causing a decrease in sensitivity. Suitability can be further enhanced.

"G. Image forming method and plate making process"
When the photosensitive material using the photosensitive composition of the present invention is used as an image forming material, usually, after image exposure, an unexposed portion of the photosensitive layer is removed with a developer to obtain an image. As a preferable developer when using these photopolymerizable compositions in the preparation of a lithographic printing plate, a developer as described in JP-B-57-7427 may be mentioned. Sodium silicate, silicate Potassium, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. An inorganic alkali agent such as this and an aqueous solution of an organic alkali agent such as monoethanolamine or diethanolamine are suitable. It is added so that the concentration of such an alkaline solution is 0.1 to 10% by mass, preferably 0.5 to 5% by mass.

  Such an alkaline aqueous solution may contain a small amount of a surfactant, an organic solvent such as benzyl alcohol, 2-phenoxyethanol, and 2-butoxyethanol as necessary. Examples thereof include those described in US Pat. Nos. 3,375,171 and 3,615,480.

  Further, the developers described in JP-A-50-26601, 58-54341, JP-B-56-39464, and 56-42860 are also excellent.

  As a particularly preferred developer, a nonionic compound represented by the following formula (IV) described in JP-A No. 2002-202616 is contained, the pH is 11.5 to 12.8, and 3 to 3 Examples thereof include a developer having a conductivity of 30 mS / cm.

          A-W (IV)

In the formula, A represents a hydrophobic organic group having a log P of AH of 1.5 or more, and W represents a nonionic hydrophilic organic group having a log P of W-H of less than 1.0.
This developer component is described in detail in paragraphs (0024) to (0067) of JP-A No. 2002-202616.

  In the present invention, it is effective to add the nonionic compound represented by the general formula (IV) in the developing solution in an amount of 0.1 to 15% by mass, preferably 1.0 to 8.0% by mass.

  In addition, as the plate making process of the lithographic printing plate precursor according to the present invention, the entire surface may be heated before exposure, during exposure, and between exposure and development, if necessary. By such heating, an image forming reaction in the photosensitive layer is promoted, and advantages such as an improvement in sensitivity and printing durability and a stabilization of sensitivity may occur. Further, for the purpose of improving the image strength and printing durability, it is also effective to carry out whole surface post-heating or whole surface exposure on the developed image. Usually, heating before development is preferably performed under mild conditions of 150 ° C. or less. When it is 150 ° C. or lower, the problem of fogging does not occur in the non-image area. Very strong conditions are used for heating after development. Usually, it is the range of 200-500 degreeC. When the temperature is 200 ° C. or higher, sufficient image strengthening action can be obtained.

  As a method for exposing a scanning exposure lithographic printing plate according to the present invention, a known method can be used without limitation. Desirably, the wavelength of the light source is 350 nm to 450 nm, and specifically, an InGaN-based semiconductor laser is suitable. The exposure mechanism may be any of an internal drum system, an external drum system, a flat bed system, and the like. In addition, the photosensitive layer component of the present invention can be made soluble in neutral water or weak alkaline water by using a high water-soluble component. After loading on top, a system such as exposure-development can be performed on the machine.

  As an available laser light source of 350 to 450 nm, the following can be used.

As a gas laser, Ar ion laser (364 nm, 351 nm, 10 mW to 1 W), Kr ion laser (356 nm, 351 nm, 10 mW to 1 W), He—Cd laser (441 nm, 325 nm, 1 mW to 100 mW), and solid laser as Nd: YAG combination of (YVO ₄₎ and SHG crystal × 2 times (355nm, 5mW~1W), Cr: LiSAF combined with an SHG crystal (430nm, 10mW), a semiconductor laser system, KNbO ₃ ring resonator (430 nm, 30 mW) A combination of a waveguide type wavelength conversion element and AlGaAs, InGaAs semiconductor (380 nm to 450 nm, 5 mW to 100 mW), a combination of a waveguide type wavelength conversion element, AlGaInP and AlGaAs semiconductor (300 nm to 350 nm, 5 mW to 100 mW), AlGaInN (350 nm) ~ 450nm, 5mW ~ 30mW), other, N ₂ laser as pulse laser (337 nm, pulse 0.1~10mJ), XeF (351nm, pulse 10 to 250 mJ), and the like.

  Among these, an AlGaInN semiconductor laser (commercially available InGaN-based semiconductor laser 400 to 410 nm, 5 to 30 mW) is preferable in terms of wavelength characteristics and cost.

  Further, as the lithographic printing plate exposure apparatus of the scanning exposure method, there are an inner drum method, an outer drum method, and a flat bed method as an exposure mechanism, and all of the light sources other than the pulse laser can be used as the light source. . Practically, the following exposure apparatus is particularly preferable in terms of the relationship between the photosensitive material sensitivity and the plate making time.

・ Single beam exposure system that uses one gas laser or solid-state laser light source with internal drum system ・ Multi-beam exposure system that uses many (10 or more) semiconductor lasers with flat bed system ・ Many semiconductor lasers with external drum system Multi-beam exposure equipment used (10 or more)

In the laser direct-drawing lithographic printing plate as described above, the photosensitive material sensitivity X (J / cm ² ), the photosensitive material exposure area S (cm ² ), the power q (W) of one laser light source, the laser Equation (eq1) is established between the number n and the total exposure time t (s).
X · S = n · q · t (eq1)

i) In the case of the internal drum (single beam) method, the laser rotation speed f (radians / s), the sub-scanning length Lx (cm) of the photosensitive material, the resolution Z (dots / cm), and the total exposure time t (s) In general, equation (eq2) holds.
f · Z · t = Lx (eq2)
ii) In the case of the external drum (multi-beam) system, the drum rotation speed F (radians / s), the photosensitive material sub-scanning length Lx (cm), the resolution Z (dots / cm), the total exposure time t (s), the number of beams In general, equation (eq3) holds during (n).
F · Z · n · t = Lx (eq3)
iii) In the case of the flat bed (multi-beam) system, the polygon mirror rotation speed H (radians / s), the photosensitive material sub-scanning length Lx (cm), the resolution Z (dots / cm), the total exposure time t (s), Equation (eq4) is generally established between the number of beams (n).
H.Z.n.t = Lx (eq4)

The resolution (2560 dpi) required for the actual printing plate, the plate size (A1 / B1, sub-scan length 42 inch), the exposure conditions of about 20 sheets / hour and the photosensitive properties (photosensitive wavelength, By substituting (sensitivity: about 0.1 mJ / cm ² ) into the above formula, it can be understood that a combination with a multi-beam exposure system of a semiconductor laser is more preferable in the photosensitive material of the present invention. Further, by combining operability, cost, etc., a combination with an external drum type semiconductor laser multi-beam exposure apparatus is most preferable.

  Further, as other exposure light for the photosensitive composition according to the present invention, ultrahigh pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various visible and ultraviolet laser lamps. Fluorescent lamps, tungsten lamps, sunlight, etc. can also be used. Moreover, as a use of the photosensitive composition by this invention, it can apply without a restriction | limiting to what is widely known as a use of photocurable resin besides the planographic printing plate for scanning exposure. For example, by applying to a liquid photopolymerizable composition used in combination with a cationically polymerizable compound as required, a highly sensitive optical modeling material can be obtained. Further, a hologram material can be obtained by utilizing a change in refractive index accompanying photopolymerization. It can be applied to various transfer materials (peeling sensitive material, toner developing sensitive material, etc.) by utilizing the change in surface tackiness due to photopolymerization. It can also be applied to photocuring of microcapsules. It can also be applied to the production of electronic materials such as photoresists, and photocurable resin materials such as inks, paints and adhesives.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.

[Synthesis example 1 of specific cyclohexyl group-containing compound A]
20.0 g of 1,4-cyclohexylene diisocyanate and 31.1 g of 2-hydroxyethyl methacrylate were dissolved in 80 ml of tetrahydrofuran and stirred, and 100 ml of di-n-butyltin dilaurate was added dropwise. Then, after stirring at room temperature for 1 hour, the precipitated crystals were filtered, and the residue was washed with 100 ml of methanol to obtain 8.5 g of Compound A4.

[Synthesis example 2 of specific cyclohexyl group-containing compound B]
By using 23.4 g of 1,3-bis (isocyanatomethyl) -cyclohexane in place of 1,4-cyclohexylene diisocyanate in the same manner as in Synthesis Example 1, 50.4 g of compound B was obtained.

[Synthesis example 3 of specific cyclohexyl group-containing compound C]
By using 28.0 g of the following 2-hydroxyethyl acrylate instead of 2-hydroxyethyl methacrylate in the same manner as in Synthesis Example 2, 50.1 g of Compound C was obtained.

[Synthesis example 4 of specific cyclohexyl group-containing compound D]
20.0 g of 1,4-cyclohexanedimethanol and 43.0 g of 2-methacryloylethyl isocyanate were dissolved in 200 ml of tetrahydrofuran and stirred, and 100 ml of di-n-butyltin dilaurate was added dropwise. After stirring at room temperature for 1 hour, the precipitated crystals were filtered, and the residue was washed with 100 ml of methanol to obtain 55.1 g of Compound D.

[Synthesis example 5 of specific cyclohexyl group-containing compound E]
20 g of cyclohexanebismethylamine and 54.3 g of 2-methacryloylethyl isocyanate were dissolved in 80 ml of tetrahydrofuran and stirred, and 100 ml of di-n-butyltin dilaurate was added dropwise. Then, after stirring at room temperature for 1 hour, the precipitated crystals were filtered, and the residue was washed with 100 ml of methanol to obtain 68.5 g of Compound E.

[Synthesis example 6 of specific cyclohexyl group-containing compound F]
By using 20.0 g of 1,4-dichlorohexanediamine instead of cyclohexanebismethylamine in the same manner as in Synthesis Example 5, 72.2 g of Compound F was obtained.

[Synthesis example 7 of specific cyclohexyl group-containing compound G]
20 g of cyclohexane bismethylamine and 40.0 g of glycidyl methacrylate were dissolved in 80 ml of dimethyl sulfoxide, 50 mg of hydroquinone was added, and the mixture was stirred at 80 ° C. for 5 hours. Water was added to the reaction solution, extracted with ethyl acetate, magnesium sulfate was added and dried, and then the solvent was distilled off under reduced pressure. Further purification by silica gel column chromatography gave 40.6 g of compound G.

[Synthesis example 8 of specific cyclohexyl group-containing compound H]
20.0 g of 1,3-cyclohexanedicarboxylic acid and 33.0 g of glycidyl methacrylate were dissolved in 80 ml of dimethyl sulfoxide, 50 mg of hydroquinone and 300 mg of N, N-dimethyldodecylamine were added, and the mixture was stirred at 100 ° C. for 5 hours. 100 ml of water was added to the reaction solution, and the mixture was extracted with ethyl acetate. After drying and evaporating the solvent, the residue was purified by silica gel column chromatography to obtain 42.4 g of Compound H.

[Synthesis Example 9 of Compound I Containing Specific Cyclohexyl Group]
20.0 g of 4,4′-methylenebiscyclohexyl isocyanate and 19.8 g of 2-hydroxyethyl methacrylate were dissolved in 80 ml of tetrahydrofuran and stirred, and 100 ml of di-n-butyltin dilaurate was added dropwise. Then, after stirring at room temperature for 1 hour, the precipitated crystals were filtered, and the residue was washed with 100 ml of methanol to obtain 36.5 g of Compound I.

[Synthesis Example 10 of specific cyclohexyl group-containing compound J]
20.0 g of cis-1,2-cyclohexanedimethanol and 43.0 g of 2-methacryloylethyl isocyanate were dissolved in 80 ml of tetrahydrofuran and stirred, and 100 ml of di-n-butyltin dilaurate was added dropwise. Then, after stirring at room temperature for 1 hour, the precipitated crystals were filtered, and the residue was washed with 100 ml of methanol to obtain 58.5 g of Compound J.

[Synthesis example 11 of specific cyclohexyl group-containing compound K]
The product was dissolved in 20.0 g of 4,4′-isopropylidenedicyclohexanol and 25.8 g of 2-methacryloylethyl isocyanate, and stirred at 80 ° C. for 6 hours. After cooling to room temperature, the produced crystals were filtered, and the residue was washed twice with 30 ml of water and then once with 20 ml of methanol to obtain 40.8 g of Compound K.

[Synthesis example 12 of specific cyclohexyl group-containing compound L]
By using 82.0 g of the following polyfunctional methacrylate alcohol in place of 2-hydroxyethyl methacrylate in the same manner as in Synthesis Example 2, 60.5 g of Compound L was obtained.

[Example of support production]
(Support 1: Production of anodized aluminum support)
An aluminum plate made of material 1S having a thickness of 0.30 mm was used with a No. 8 nylon brush and an aqueous suspension of 800 mesh Pamiston, and its surface was grained and washed thoroughly with water. After etching by immersing in 10% sodium hydroxide at 70 ° C. for 60 seconds, washed with running water, neutralized with 20% HNO ₃ and washed with water. This was subjected to an electrolytic surface roughening treatment in a 1% nitric acid aqueous solution with a anodic electricity quantity of 300 coulomb / dm ² using a sinusoidal alternating current under the condition of VA = 12.7V. When the surface roughness was measured, it was 0.45 μm (Ra indication). Next, after dipping in a 30% H ₂ SO ₄ aqueous solution and desmutting at 55 ° C. for 2 minutes, a cathode was placed on the grained surface in 33 ° C., 20% H ₂ SO ₄ aqueous solution to obtain a current density. When anodized at 5 A / dm ² for 50 seconds, the thickness was 2.7 g / m ² . This was designated as Support 1.

(Manufacture of support body 2)
The support 2 was prepared by applying the following surface-treating undercoat liquid composition 2 to the support 1 so that the Si amount was about 0.001 g / m 2 and drying at 100 ° C. for 1 minute.

<Liquid composition 2 for undercoat>
The following components were mixed and stirred. After about 5 minutes, heat generation was observed, and after 60 minutes of reaction, the contents were transferred to another container, and further 30,000 parts by mass of methanol was added to make liquid composition 2.

Unichemical Co., Ltd. Phosmer PE 20 parts by weight Methanol 130 parts by weight Water 20 parts by weight Paratoluenesulfonic acid 5 parts by weight Tetraethoxysilane 50 parts by weight 3-Methacryloxypropyltriethoxysilane 50 parts by weight

(Manufacture of support body 3)
To the support 1, methyl methacrylate / ethyl acrylate / 2-acrylamido-2-methylpropanesulfonic acid sodium copolymer (60/25/15 molar ratio, molecular weight Mn = 30,000), water / methanol = 5 g / 95 g A support 3 was obtained by coating the solution dissolved in 1 to a coating amount of 3 mg / m ² and drying at 80 ° C. for 30 seconds.

[Example of production of lithographic printing plate precursor]
On the above-mentioned supports 1 to 3, a photosensitive composition having the following composition was applied so that the dry coating mass was the amount shown in Table 1, and dried at 95 ° C. to form a photosensitive layer.

(Photosensitive layer coating solution (photopolymerizable composition): Details are given in Tables 1 and 2 below)
Cyclohexyl group-containing compound or comparative compound of the present invention Table 2 Binder polymer (B) Table 1 sensitizer (D) 0.10 parts by mass Initiator (I) 0.05 parts by mass Co-sensitizer or additive ( H) 0.25 parts by mass Fluorosurfactant 0.02 parts by mass (Megafac F-177: manufactured by Dainippon Ink & Chemicals, Inc.)
Thermal polymerization inhibitor 0.03 parts by mass (N-nitrosohydroxylamine aluminum salt)
ε-type copper phthalocyanine dispersion 0.2 parts by mass Methyl ethyl ketone 16.0 parts by mass Propylene glycol monomethyl ether 16.0 parts by mass

  Comparative compounds M, N, O, binder polymer (B), sensitizer (D), polymerization initiator (I), and additive (H) used in the photosensitive layer coating solution are shown below.

"Coating of protective layer"
On this photosensitive layer, a 3% by weight aqueous solution of polyvinyl alcohol (saponification degree 98 mol%, polymerization degree 550) was applied so that the dry coating weight was 2 g / m 2 and dried at 100 ° C. for 2 minutes.

(exposure)
Exposure 1 (photosensitive layers 1-4, 6, 7)
Each lithographic printing plate precursor having photosensitive layers 1 to 4, 6, and 7 is solid with a violet LD having a wavelength of 405 nm (a violet boxer manufactured by FFEI) at an exposure amount of 50 μJ / cm 2 and 175 lines / inch at 4000 dpi. The image and a 1 to 99% halftone dot image (in 1% increments) were subjected to scanning exposure.
Exposure 2 (photosensitive layer 5)
A lithographic printing plate precursor having the photosensitive layer 5 is printed with a solid image and 1 to 99 on an FD • YAG laser (CSI, plate jet 4, 532 nm) at an exposure amount of 100 μJ / cm 2 at 4000 dpi and 175 lines / inch. % Dot image (in 1% increments) was scanned and exposed.

(developing)
Standard processing was performed with an automatic processor (Fuji Photo Film LP-850P2) charged with Developer 1 (or 2) and Finishing Gum Solution FP-2W (Fuji Photo Film). The preheating conditions were a plate surface temperature of 100 ° C., a developer temperature of 30 ° C., and an immersion time in the developer of about 15 seconds.
Developers 1 and 2 have the following composition, pH is 11.5 (developer 1) and 12.3 (developer 2) at 25 ° C., respectively, and conductivity is 5 mS / cm (developer 1). 17 mS / cm (Developer 2).

(Composition of Developer 1)
Potassium hydroxide 0.15g
Polyoxyethylene phenyl ether (n = 13) 5.0 g
Kirest 400 (chelating agent) 0.1 g
94.75 g of water

(Composition of Developer 2)
1K-potassium silicate 2.5 g
Potassium hydroxide 0.15g
Polyoxyethylene phenyl ether (n = 13) 5.0 g
Kirest 400 (chelating agent) 0.1 g
92.25 g of water

[Evaluation of printing etc.]
The sensitivity, storage stability, printing durability, and stain resistance of the lithographic printing plate precursor obtained above were evaluated by the following methods. The results are summarized in Tables 2-8.

(Evaluation of sensitivity)
The printing plate is exposed under the respective conditions, and immediately after that, it is developed under the conditions described in Tables 2 to 8 to form an image. At that time, the area percentage of 50% halftone dot is measured by a halftone dot area measuring device (Gretag-Macbeth). ). The larger the number, the higher the sensitivity.

(Image area printing durability test)
R201 manufactured by Roland was used as the printing machine, and GEOS-G (N) manufactured by Dainippon Ink was used as the ink. The printed matter in the solid image area was observed, and the printing durability was examined based on the number of sheets on which the image began to fade. The higher the number, the better the printing durability.

(Half dot printing durability test)
R201 manufactured by Roland was used as the printing machine, and GEOS-G (N) manufactured by Dainippon Ink was used as the ink. On the 5000th sheet from the start of printing, PS plate cleaner CL-2 manufactured by Fuji Photo Film Co., Ltd. was soaked in a printing sponge, the halftone dots were wiped, and the ink on the printing plate was washed. Thereafter, 10,000 sheets were printed, and the presence or absence of halftone dots in the printed matter was visually observed.

(Non-image area stain resistance test)
R201 manufactured by Roland was used as the printing machine, and GEOS-G (S) manufactured by Dainippon Ink was used as the ink. The printed matter in the non-image area (unexposed area) was observed to evaluate the stain resistance.

(Evaluation of storage stability)
The halftone dot area was measured in the same manner as in the sensitivity evaluation except that the lithographic printing plate precursor was sealed with aluminum kraft paper together with interleaving paper and allowed to stand at 60 ° C. for 4 days. Next, the difference between the halftone dot area with a standing at 60 ° C. for 4 days and the halftone dot area with no standing at 60 ° C. for 4 days was taken, and the change in halftone dot (Δ%) due to forced aging was measured. The smaller the absolute value of this number, the less the influence of forced aging, that is, the higher the storage safety.
The results are shown in Tables 2-8.
In Examples 1-60 are reference examples.

  As is apparent from Tables 2 to 8, in the lithographic printing plate precursors of the respective examples to which a cyclohexyl group-containing compound is added, which is a feature of the present invention, both sensitivity and storage stability are achieved, and printing durability Although satisfactory results were obtained in terms of stain resistance, no practical lithographic printing plate could be obtained with the lithographic printing plate precursors of the comparative examples.

Claims (4)

(A) a compound represented by the following general formula (I),
(B) a polyurethane containing 10 wt% or more of aromatic groups,
A lithographic printing plate precursor having a photosensitive layer containing a polymerization initiator represented by the following formula I2 and a photosensitive composition containing a thiol or sulfide as a co-sensitizer.

(In the formula, m represents an integer of 2 to 6, l represents an integer of 0 to 6, X represents each independently a divalent linking group, and n represents each independently an integer of 0 or more. Each independently represents a hydrogen atom or a methyl group, and each Z independently represents a monovalent substituent, and when m or l is an integer of 2 or more, X, n, R, Z May be the same or different.)

  The lithographic printing plate precursor according to claim 1, further comprising a protective layer on the photosensitive layer. The co-sensitizer is 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto -4 (3H) - according to claim 1 or 2 quinazoline or β- -mercaptonaphthalene A lithographic printing plate precursor. The lithographic printing plate precursor as claimed in claim 3 , wherein the co-sensitizer is a compound represented by the following formula H4.